Chemical and metallurgical aspects of arsenical bronze: the case of arsenic-loss in prehistoric metal production

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Arsenic poisoning

An alternative usage of arsenic as described by Georg Kreisler (information in English) in his black humour chanson ‘Tauben vergiften‘ [poisoning pigeons] due to the high number of pigeons in Vienna in the 1950ies.

Slightly over a century ago, poison was a common part of everyday life. Arsenic, the notorious metalloid, was used in all sorts of products, primarily in the inks and aniline dyes of beautifully printed wallpapers and clothing. Odorless and colorless, it went into food as food coloring, and it was used in beauty products, such as arsenic complexion wafers that promised women pure white skin, until as late as the 1920s. It was found in the fabric of baby carriages, plant fertilizers, medicines. It even was taken as a libido pill in Austria.

The literature of the era hints at the effects from arsenic poisoning. The main character in Charlotte Perkins Gilman’s 1892 short story “The Yellow Wallpaper,” for instance, descends into madness and believes that the source of her illness stems from the wallpaper in her room. “It makes me think of all the yellow things I ever saw—not beautiful ones like buttercups, but old foul, bad yellow things,” she says. “But there is something else about that paper—the smell!”There are numerous studies on William Morris’s arsenic-laden wallpapers, in particular, which were extremely popular during the late 19th century. Morris himself, a designer and artist, was also the heir to the world’s largest copper mine at the time, which produced arsenic dust due to mining activity. Not only did the mine cause massive environmental damage to the land around it, but many miners died of lung disease, according to a 2003 article in Nature. Morris’s famous phrase about the doctors who treated these miners was that they “were bitten by witch fever,” insinuating that the doctors were quacks when they diagnosed arsenic poisonings. He was unwilling to believe the catastrophe his businesses had caused.
As long as people get what they want, most people don’t think twice about it.

Using Morris’s phrase as a fitting title, the art historian and Victorianist Lucinda Hawksley’s new book, Bitten by Witch Fever, tells the story of the extensive use of arsenic in the 19th century. It includes pictures of objects and artworks made from substances that incorporated arsenic, and advertisements for arsenic-filled products for Victorian women, such as soap with a doctor’s certificate to ensure its harmlessness.I spoke to Hawksley about arsenic’s prevalence in 19th-century home decoration, clothing, food, and topsoil. Our conversation has been condensed and edited for clarity.

Haniya Rae: Why was arsenic so commonly used?Lucinda Hawksley: In mid-Victorian times, Pre-Raphaelite and Aesthetic artists were particularly sold on this vivid shade of green, found by the Swedish chemist Carl Wilhelm Scheele in the 18th century. The green color came from copper arsenite, known as Scheele’s Green, which is a form of arsenic and a byproduct of the copper industry.If you think about the brilliance of copper and the way that a patina begins to color metal, it’s a beautiful color. Chemists hadn’t thought about how poisonous arsenic was, which today would seem crazy to us—it was present in so many things. Victorians didn’t think it was a problem unless you ate it. They hadn’t made the connection that the same thing that created this amazing green, and that was immensely fashionable in the 1860s and 1870s, could be a problem. It wasn’t just the Victorians, though—Germany, the United States, Scandinavia, among others, were all using arsenic in common goods.

Rae: By the late Victorian period, though, people had started to figure out it was dangerous?Hawksley: Around the 1860s, the cases of arsenic poisoning started getting to the newspapers. One wallpaper manufacturer debuted arsenic-free wallpaper, but no one paid much attention to that, until more and more cases started appearing. By the 1870s, William Morris started to produce arsenic-free wallpapers. At this point, William Morris himself didn’t actually believe that the arsenic was the problem—he was simply bowing to public pressure. He thought because no one was ill in his house from the arsenic wallpaper, it must be something else that was causing the sickness.

Rae: What were a few of these cases?Hawksley: Factory workers were getting sick—and many died—because they were working with green arsenic dye. It was fashionable to wear these artificial green wreaths of plants and flowers in your hair that were dyed with arsenic. In wallpaper factories, workers were becoming really unwell, especially when they were working with flock papers, or papers with small fiber particles that stick to the surface. The workers would dye these tiny, tiny pieces of wool or cotton in green, and while doing so would inhale them and the particles would stick to their lungs. The manufacturing process created a lot of dust from the dye—the dust had arsenic in it—and this created major problems for the factory workers as the dust would stick to their eyes and skin. If there were abrasions on their skin, the arsenic could get directly into their blood stream and poison them that way as well.

When the newspapers started to point out that this was happening, most people didn’t care. It’s a bit like today. People will still buy a brand of chocolate even if there’s been a story on how the chocolate has been produced by slave labor. They buy coffee that was also produced by slaves. They buy clothes, even though it was made by bonded labor. As long as people get what they want, most people don’t think twice about it. If they were confronted with things face on, of course they wouldn’t buy these products.

Rae: Did Britain ever pass legislation about arsenic?

Hawksley: In 1903 century, the U.K. actually did pass legislation about the safe levels of arsenic levels in food and drink—even though often there are no safe levels at all—but Britain never passed laws around wallpaper or paint. By the time the regulations were passed on arsenic in food and drink, arsenic wallpaper and paint had fallen out of fashion, so it’s possible they didn’t see a reason to actually pass legislation against it. To this day, there still isn’t a law banning someone from making arsenic wallpaper or dye in Britain.Rae: But it was pretty bad before that point?Hawksley: Before legislation was passed, bakers used arsenic green as a popular food coloring. Sometimes, a baker was given flour or sugar with arsenic in it unknowingly, but other times it was used as a bulking agent. You wouldn’t believe the kinds of things that were put into Victorian foods as bulking agents. It wasn’t just arsenic, there were lots of weird things. Flour was expensive, so they would resort to adding other things.There was an orphanage in Boston and all these small children were getting really, really sick and they didn’t know why. It turned out that the nurses were wearing blue uniforms dyed with arsenic and they were cradling the children, who in turn were inhaling the dye particles.That’s another thing, too: Green was a color that was always seen as the culprit, simply because it was so desirable at the time, but many other colors used arsenic as well. When the National Archives did testing on the William Morris wallpapers, all of the colors used arsenic to some extent. These colors were exceptionally beautiful, and up until this point, it was not something they could achieve without the use of arsenic.Rae: Are there still remnants of arsenic mining today?Hawksley: It’s funny because as I was doing my research, I was having a conversation with an older woman about my work. She had memories of growing up in the 1930s near a town that had had a working copper mine nearby. Her mother had told her not to grow any vegetables, because at that time they had realized the dangers of arsenic dust and knew it was in the soil. But for a long time, people living near copper mines had no idea that arsenic dust was falling on the soil, and so their crops would absorb all this arsenic dust. Lots of people were getting sick, but no one seemed to understand why. I’m sure that must have been the case with mining like this all over the world.

This time, it is bacteria eating arsenic. To be more precise: especially ectothiorhodospira-like purple bacteria or oscillatoria-like cyanobacteri are using arsenite as an energy source. The light-dependent oxidation of arsenite [As(III)] to arsenate [As(V)] occurrs under anoxic conditions. The recently discovered bacteria from oxygen-free hot springs in Mono Lake, California, suggest that the arsenic metabolism / photosynthesis evolved at the same time, or even before, ‘normal’ photosynthesis.

We just should not add nano-size rust particles to their food. Arsenic binds particularly well to iron oxides, or rust, and can be consequently easily removed by nano-size rust particles. Such particles can be easily produced by simmering (olive/oleic) oil and rust in a frying pan, which might be a cheap way to remove arsenic from drinking water, which presence there is still a very big problem in Bangladesh or West Bengal (and it seems also in Cornwall, UK). The clumped together arsenic and rust can be easily removed with a magnet.

Young gentoo penguins on Peterman Island (c) Wikipedia

Discussing arsenic in food and drinking water brings us consequently also to end-product of digestion. And penguins, in particular Gentoo penguins. Both together are the main source of arsenic accumulation in Antarctic soil. The droppings of this type of penguin contained far more arsenic than those of other species, such as the droppings of the southern giant petrel and up to three times more than the local seals. Consequently, the sediments of other Antarctic islands without resident penguins (but similar geology) contain half the levels of arsenic compared with sediment sampled on Ardley Island, where these penguins live. Since arsenic is present in the water, which is absorbed by krill and then accumulates in the food chain, passing to predators such as penguins, the arsenic levels measured in Antarctic soil can be used as an indicator of past (Gentoo) penguin populations: the more arsenic, the more penguins.

Being beautiful in Victorian England was not healthy, especially for those wishing to obtain a “natural” look: washing the face with ammonia, opium masks overnight, mercury eye treatment, arsenic skin whiteners… others, following the “painted” look, were not better off: using lead paint destroyed their skin and had various other side effects on their health.

All to fullfill the ideal look of the consumptive with watery eyes, pale and traslucent skin. Shortly, the closer the skin resembled that of a corpse, the better it was. One could achieve that look by a “natural” way, or by painting yourself. While the latter included for the average lady several quite “unnatural treatments”, the “painted” lady coated their faces and arms with white paints and enamels. Unfortunately, these paints were made from lead, which is highly corrosive. That means, you need to use more paint every time, since it destroyed your skin underneath. One might then paint veins on the enamel e.g. with indigo dye veins.

To look almost dead, arsenic was quite helpfull (it’s all about the dose!): nibbling on Arsenic Complexion Wafers was considered as “perfectly harmless” and used widely. Of course the toxity of arsenic was known (it was commonly used by murderesses of the era), but, since it was so effective in skin lightening, its usage continued for decades. Also, it was said to remove pimples, clear the face of freckles and tan and will make you a charm of person and simply adorable. Needless to say, that you also had to use arsenic soap and shampoo.

Lola Montez describes in her “The Arts of Beauty” women in Bohemia taking baths in arsenic springs, and drinking the water, “which gave their skins a transparent whiteness“. But, as she continues, there are also side effects: “for when once they habituate themselves to the practice, they are obliged to keep it up for the rest of their days, or death would speedily follow“. One might think of the japanese self-mummified monks (known as sokushinbutsu), followers of shugendō, an ancient form of Buddhism, who died in the ultimate act of self-denial. Apart their diet, a local spring containing high levels of arsenic may have helped the monks in the mummification process.

Arsenic was simply everywhere in Victorian England: apart cosmetics, and medicines, it was in the food, on the walls, and in textiles. The German scientist Frederik Accum was fed up with the manipulation of the food industry in London and published his A Treatise on Adulterations of Food and Culinary Poisons. In the book, he noted for instance the contamination of wine with arsenic. So also the glass of wine you were nipping off at your ball in Victorian England was probably full of arsenic.

The Arsenic Waltz or The New Dance of Death (1862 issue of Punch; Photo: Wellcome Library, London/Courtesy Bloomsbury)

Hopefully you were not wearing any green dress? Green ball gowns were usually tinted with arsenic. I don’t want to imagine the health condition of the persons making these dresses, but contemporary chromolithograph showing the effect of arsenic used in artificial flowermaking on workers’ hands may give an impression.

Beauty standards for women existed already in the Middle Ages; white skin and a high forehead were just a few of them. To get rid of disturbing facial hair, women used razors, tweezers, bees wax, or pumice stone. However, one could also eliminate the hair with a highly alkaline solution made of calcium oxide (quicklime) and orpigment (arsenic trisulfide), mixed with water and oil. This alkaline solution melts the hair from the skin’s surface. In Europe, its oldest recipe can be found in the 12th century Trotula. The recipe’s origin is in the Near East, where it is known as rhusma turkorum.

Variations of it can be found in many other mediaeval and renaissance beauty books. Alternatives were probably less dangerous, but surely more creative: they included ingredients such as dog milk, boiled leeches, burnt and powdered young doves, bat blood, and others (Nürnberg, Stadtbibliothek, Cod. Amb. 55, Nr. 37; Karlsruhe, Kodex St. Georgen 73, fol. 205v und 214r).

One might think that the arsenic-rich way of hair removal was not in use for long, especially taking into account the risk of your flesh coming off, as indicated by a book from the 16th century on how to remove or lose body hair: “boil one pint of arsenic and eight pints of quicklime. Go to a bath or hot room and place the mixture on the body, where you want to remove the hair. When the skin feels hot, wash it quickly with hot water, so your flesh does not come off”.

Surprisingly, the most recent recipe I found dates from the beginning of the 20th century AD (Italian manual “per esser belle”, Sonzogno/Milan, 1906): 40g calcium oxide, 5g arsenic, a bit of soap, and one yolk are mixed together, and then applied on the skin for one hour. One may then rub some olive oil on the skin. After washing, the hairs fall off (let’s hope just the hair, and not your flesh).

On average, American red wine has more than twice the arsenic level allowed in drinking water.

Arsenic and old lace

A new University of Washington study that tested 65 wines from America’s top four wine-producing states (California, Washington, New York and Oregon) found all but one have arsenic levels that exceed what’s allowed in drinking water (which is 10 parts per billion of arsenic). The wine samples ranged from 10 to 76 parts per billion, with an average of 24 parts per billion. But also other products, such as apple juice, rice, or cereal bars, are high in arsenic or contain significant amounts of arsenic (milk, bottled water, infant formula, salmon and tuna).

“Unless you are a heavy drinker consuming wine with really high concentrations of arsenic, of which there are only a few, there’s little health threat if that’s the only source of arsenic in your diet,” said Wilson.

But it’s not just the red wine.

“consumers need to look at their diets as a whole. If you are eating a lot of contaminated rice, organic brown rice syrup, seafood, wine, apple juice — all those heavy contributors to arsenic poisoning — you should be concerned, especially pregnant women, kids and the elderly,” so Wilson.

The food that posed the largest risk of arsenic poisoning was infant formula made with organic brown rice syrup, an alternative to high-fructose corn syrup. Wilson estimated that some infants eating large amounts of certain formulas may be getting more than 10 times the daily maximum dose of arsenic.

As early as the 12th century AD and presumably until shortly before the Second World War, some inhabitants of Styria and the mountainous regions of Tyrol consumed high quantities of arsenic (also called Hidrach, Hittrach = Hüttenrauch, which means ‘smoke of the hut’) by licking it like a candy or placing arsenic powder on speck or bread. Although a dose of 0.1 mg As is usually fatal, arsenic-eaters may ingest up to three or four times this quantity without severe poisoning. However, rather than becoming tolerant, it appears that absorption in the stomach and intestines is reduced as arsenic-eaters showed typical symptoms of poisoning once arsenic was injected.

Arsenic eaters are reported to have consumed up to 0.3-0.4 mg of arsenic trioxide over longer periods (30 years or more). Some of them consumed ‘artificial orpiment’, which contains up to 90% arsenic trioxide, produced by melting the oxide with sulfur. Generally, Arsenic eaters began by consuming small amounts of arsenic, typically about 10 mg, which they increased every 2 or 3 days up to 0.3-0.4 mg (Przygoda et al. 2001). Accidental poisonings were rare due to the detailed knowledge and the fact that the ‘expertise’ developed was passed on in the family.

A typical description of one of the arsenic-eaters, as documented by K.H. Most and published by Przygoda et al. 2001, figure 1.

The existence of arsenic-eaters is the origin of the so-called ‘Styrian-defense’: not only in Austria, but for instance also in the UK, trials dealing with arsenic poisoning had to consider if the victim might have been an arsenic-eater. In the Victorian era arsenic was easily available and practically everywhere: in dresses, wallpaper, food (arsenic was used as a colorant), cosmetic products, confections, medication, and so on.

In addition to a small number of Austrians in some mountainous regions, Mithridates VI, Darwin, Napoleon*, and Queen Victoria are known to have regularly consumed arsenic to prevent poisoning, as well as for its (initially) positive effects: a warm feeling in the stomach due to an irritation of the lining of the stomach (similar as it happens during the consumption of alcohol), increased appetite and well being (consequently, people gain weight) and last, but not least, due to its performance-enhancing (also sexually) characteristics.

With increased consumption, the negative effects prevail (see the previous post and this presentation)

Not only humans consumed arsenic: from the 17th century onwards, it was regularly given to horses prior to sale, giving them the appearance of being healthier, younger and more vital with a shiny coat due to the increased amount of oxygen in the blood. Schulz 1939 noted that the regular consumption of arsenic also affects the growth of bones; pregnant animals given arsenic usually died during birth since the young were far too big to pass through the pelvis.

* Napoleon was most likely not poisoned with arsenic; the fact that his hair (if it is even his hair) contains high levels of arsenic might be due to conservation using arsenic. Also, he might have used Fowler’s solution extensively. Furthermore, it is known that his green wall paper contained arsenic; this, together with mildew, may have resulted in the formation of organic arsenic compounds which might have also contributed to his death.

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Marianne Mödlinger

Marianne Mödlinger is a prehistoric archaeologist. Her main research interests include Bronze Age studies, the manufacture and usage of Bronze Age arms and armour, archaeometallurgy of copper alloys, and experimental archaeology.